Abstract: The preparation of nanogold / thionine multilayer film modified glassy carbon electrode and the electrochemical behavior of nitrite on this electrode were studied. The glassy carbon electrode was activated by potentiostatic method in dilute nitric acid solution to generate oxygenbearing groups (such as -COH) on electrode surface. Then, the electrode was immersed in thionine solution. The schiff alkali reaction occurred between -NH2 in thionine with -COH on glassy carbon electrode surface to immobilize of thionine on electrode. Finally, the nanogold was modified on the surface of the electrode immersed in a nanogold solution by interreaction of nano-gold with thionine, realizing the preparation of nanogold / thionine multilayer film modified glassy carbon electrode. The experimental results showed that, this modified electrode could significantly accelerate the electrochemical process of nitrite on electrode surface. The electrochemical response signal was linear to the concentration of nitrite in range of 2×10-6 -50×10-5 mol/L and 50×10-5-20×10-3 mol/L. The detection limit of nitrite was 5×10-8 mol/ L (S/N=3).The proposed method was applied to the determination of nitrite in water samples with relative standard deviations of 2.2%-3.2% and recoveries of 98%-104%.